Total Reflection XRay Fluorescence Spectroscopy Working Principles

ISSN: 2348 9510
International Journal Of Core Engineering &Management (IJCEM)

Volume 1, Issue 5, August 2014

36

Total Reflection X-Ray Fluorescence Spectroscopy -Working
Principles

Ashok Kumar Gupta
Assistant Professor& HOD - Mechanical Engineering,
Rishiraj Institute of Technology, Indore (M P) 453331
Email: ashokgagorni@gmail.com

Abstract:
The total reflection X-ray fluorescence (TXRF) method has been used for the analysis of
various types of solid materials of biological, geological and environmental origin. X-ray
Fluorescence Spectroscopy (XRF) has reached the stage where it is classified as a mature
analytical technique. The theoretical principles are well understood. In addition modern
instrumentation demonstrates enhanced generator and temperature stabilit y. High
sensitivity is possible even for light elements and effective matrix correction software is
available to the modern day spectroscopist. Apart from its continued applications in
research and development, XRF has become a routine process control tool.
X-ray Powder diffraction (XRD), on the other hand, has with minor exceptions as in the
cement industry, largely remained a research tool, despite being an older analytical
technique than XRF. XRD has progressed significantly in the past decade from a mainly
qualitative technique for the identification of crystalline materials to a quantitative tool
with the advance of more powerful software packages. This software has improved
instrument control, but also quantification and structure determination using the Rietveld
method. Consequently, XRD is rapidly entering the process control environment.

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This paper proposes the standardization of total reflection X-ray fluorescence (TXRF)
analysis for environmental and biological samples. The importance of TXRF in
environmental and biological analysis is now well established and it is continuously
growing. However in these fields there are not standardized methods reported by the
International Standard Organization (ISO). For this reason, the international collaboration
for the development of new standard procedures and methods for TXRF analysis is
required. Indeed, a project for Inter laboratory comparison of TXRF spectroscopy for
environmental analysis was set up in the frame of the Versailles Project on Advanced
Materials and Standards, with the aim of developing a new ISO standard for TXRF
devoted to environmental and biological analysis.
Total Reflection X-ray Fluorescence (TXRF), an advanced variant of Energy Dispersive
X-ray Fluorescence (EDXRF), is a comparatively new technique of material
characterization. The geometrical improvements in TXRF lead to betterment of detection
limits by several orders of magnitude compared to that of EDXRF. TXRF can be used
mainly in three types of applications: trace element analysis, micro analysis and depth
profiling.

Key Words: Total reflection X-ray fluorescence (TXRF), X-ray Powder diffraction
(XRD), X-ray Fluorescence Spectroscopy (XRF), Sample Preparation

Introduction:
X-ray Fluorescence Spectroscopy (XRF)
XRF is a good general purpose analytical tool that can analyze both solid and liquid
samples. It is based on the effect of the interaction of x-rays with matter, which causes
excitation of certain electrons, which when relaxing to their ground state, emit x-rays of a
characteristic wavelength for that element. This method, which can be non-destructive, is
very good for identifying impurities in metals or characterizing a particular alloy. It may
also be used for characterizing impurity levels of chemical compounds. Detection limits
vary with the nature of the sample and the elements present but usually of the order of
0.1% by weight. For solid samples, this technique can only analyze the first few hundred

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microns of the surface. For this reason, it is not suitable for inhomogeneous solid
mixtures.
Total Reflection X-ray Fluorescence Spectroscopy (TRXRF)
This method is similar to XRF except that the incident x-rays arrive at a very shallow
angle to the substrate and do not penetrate it. Instead, characteristic radiation is produced
by the very top layers of the sample including any contaminants. To be effective, the
substrates should be flat and this has led to it being adopted for the identification of
contaminants on semiconductor wafers. However, other samples may be examined
providing they are sufficiently flat. Detection limits are dependant on the elements
present but are in the ppb to ppm range.
X-ray diffraction

From powders and solids to thin films and nanomaterials
In materials research, the scientist has many analytical questions related to the crystalline
constitution of material samples. XRD is the only laboratory technique that reveals
structural information, such as chemical composition, crystal structure, crystallite size,
strain, preferred orientation and layer thickness. Materials researchers therefore use XRD
to analyze a wide range of materials, from powders and solids to thin films and
nanomaterials.

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Science and industry
Many researchers, in industrial as well as in scientific laboratories, rely on X-ray
diffraction as a tool to develop new materials or to improve production efficiency.
Innovations in X-ray diffraction closely follow the research on new materials, such as in
semiconductor technologies or pharmaceutical investigations. Industrial research is
directed towards ever-increasing speed and efficiency of production processes. Fully
automated X-ray diffraction analysis in mining and building materials production sites
results in more cost-effective solutions for production control.
Solutions for analytical questions
X-ray diffraction analysis meets many of the analytical needs of a materials scientist. In
powders, chemical phases are identified qualitatively as well as quantitatively. High-
resolution X-ray diffraction reveals the layer parameters such as composition, thickness,
roughness and density in semiconductor thin films. Small-angle X-ray scattering and pair
distribution function (PDF) analysis help to analyze the structural properties of nano
materials. Stresses and preferred orientation can be determined in a wide range of solid
objects and engineered components.
X-ray fluorescence (XRF) spectrometry is an elemental analysis technique with broad
application in science and industry. XRF is based on the principle that individual atoms,
when excited by an external energy source, emit X-ray photons of a characteristic energy
or wavelength. By counting the number of photons of each energy emitted from a sample,
the elements present may be identified and quantities.
Henry Moseley was perhaps the father of this technique, since he, building on W.C.
Rentgens discovery of the high-energy radiation dubbed X-rays, built an X-ray tube
which he used to bombard samples with high-energy electrons. Moseley in 1912
discovered a mathematical relationship between the elements emitted X-ray frequency
and its atomic number. In 1925 Coster and Nishina were the first to use primary X-rays
instead of electrons to excite a sample. After Glocker and Schreiber were the first to
perform quantitative analysis of materials using XRF in 1928, detector technology had to
catch up in order to make the technique practical, which didnt begin to happen until the
1940s. The 1950s saw the first commercially produced X-ray spectrometers. In 1970,
the lithium drifted silicon detector was developed, and this technology is still in use today
(Jenkins 1988: 51-53).

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Modern XRF instruments are capable of analyzing solid, liquid, and thin-film samples for
both major and trace (ppm-level) components. The analysis is rapid and usually sample
preparation is minimal or not required at all.
The Archaeometry Laboratory at the MU Research Reactor is the home of two Bruker
Tracer III-V handheld instruments (one equipped with an automated sample changer) and
an Elva-X benchtop instrument. These instruments are used primarily for the provenance
research on obsidian artifacts from around the world, but they are also used in special
circumstances for the non-destructive analysis of other materials such as metals, ceramic
paints, and soils.

Main principle:
The main principle of X-Ray Fluorescence Spectroscopy (XRF) is based on the fact, that
atoms, when irradiated with X-Rays, radiate secondary X-Rays the Fluorescence
radiation.
On this basis XRF-analysis is possible because:
The wavelength and energy of the Fluorescence radiation is specific for each element.
The concentration of each element can be calculated using the intensity of the
Fluorescence radiation.

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TXRF analysis using the PicoTAX:
The working principle of Total reflection X-Ray Fluorescence spectroscopy as realized
in the PicoTAX spectrometer is shown in Figure 1.

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The X-Ray beam, generated by the Molybdenum tube, is reflected on a Ni/C-multilayer
resulting in a monochromatic X-Ray beam. This small beam passes the sample holder
carrying the sample at a very small angle (0.3 0.6 ) causing total reflection of the
beam. The characteristic Fluorescence radiation emitted by the sample is detected by an
energy dispersive detector (XFlash detector) and the intensity is measured by means of
an amplifier coupled to a multi-channel analyzer.
The main difference with respect to common XRF spectrometers is the use of
monochromatic radiation and the total reflection optic. Illuminating the sample with a
totally reflected beam reduces the absorption as well as the scattering of the beam in the
sample and its matrix.

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Resulting benefits are a largely reduced background noise, and consequently much higher
sensitivities and the significantly reduction of matrix effects.
One major advantage of TXRF, compared to atomic spectroscopy methods like AAS or
ICP-OES, is the avoidance of memory effects.

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The technical parameters of the PicoTAX spectrometer are summarized in Table 1.

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Sample types and preparation:
A summary of samples types, which can be analyzed by means of TXRF is given in
Table 1, showing the great variety of applications.
For TXRF analysis all samples must be prepared on a sample tray, which reflects X-Ray
radiation. For this purpose the usage of trays with a diameter of 30mm, made of acrylic or
quartz glass is common.

Liquids can be perpetrated directly on the sample tray. An amount of several l is
transferred to the glass disc using a pipette and subsequently evaporated in desiccators or
drying oven (Figure 3).

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For solid samples different kinds of preparation are possible.
Powdered samples (suspended matter, soils, minerals, metals, pigments, biogenous solids
etc.) can be analyzed directly after preparation of the material on the sample tray.
Typically, a few g of sample material are transferred, using a Q-tip or a lint-free tissue.
In a similar way the direct preparation of single micro samples (particles, slivers etc.) is
possible.
Alternatively, powdered solids can be prepared as a suspension with volatile solvents like
acetone or methanol. The suspension is then pipetted onto the sample tray.

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In Figure 3 the sample preparation is described for solids, which were digested by
microwave digestion.
Analysis and quantification:
In general all elements starting from Sodium up to Uranium (excl. Niobium,
Molybdenum and Technetium) can be analyzed by the PicoTAX (Figure 4).

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TXRF analysis is based on internal standardization.
Therefore, an element, which is not present in the sample, must be added for
quantification (Figure 3).
The complete process of analysis and quantification is described by the following steps:
Measurement of the complete spectrum.
All detectable elements are measured simultaneously.

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Evaluation of the measured spectra
All identified elements have to be marked for further quantification, which can be done
manually or automatically by the software.
Spectra deconvolution
On the basis of the chosen elements, the software performs the deconvolution of the
spectra.
The net intensities of the element peaks are calculated with regard to corrections of line
overlaps, background factors, escape peak correction etc.
Calculation of concentrations
The element concentration is calculated by the simple formula:

where N is the net intensity, S the relative sensitivity and c the concentration - each either
of the analyte x or the internal standard is, as indicated.
The typical detection limits of the PicoTAX in aqueous solutions is presented in Figure
5.

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Summary:
The PicoTAX TXRF spectrometer is a versatile instrument for trace element analysis of
different kinds of samples. It is completely independent of any cooling media and
therefore applicable for on-site analysis.
Further benefits of the PicoTAX are the simple calibration routine, the absence of matrix
or memory effects and the ability for fast multi-element analysis.

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15. Skoog, Douglas A.; Holler, F. James; Nieman, Timothy A. Principles of
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ISSN: 2348 9510

International Journal Of Core Engineering &Management (IJCEM)

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